Composition of matter and method of making same



Patented. Apr. 10, 1945 COMPOSITIONOF MATTER ME'IHO OF MAKING SAME Melvin De Groote, University City, Bernhard Keiser, Webster Groves, and Arthur F. Wirtel, Kirkwood, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application 'lune 21, 1943, i Serial No. 491,131

4 Claims. (01.260-495) This invention relates to a new composition of 7 example, 8-10 hours: or it may be quite extensive,

matter that is capable of various uses, our presfor instance, as long as 10-12-14 days, the longer ent application being a continuation-in-part of time periods being employed generally when the our pending application Serial No. 440,749, filed temperature is just slightly above the boiling point April 27, 1942. 5 of water, and when oxidation is with air at at- The main objector our invention is to provide mospheric pressure.

a new chemical product or compound that is par- One method of preparing drastically-oxidized ticularly adapted tor use as a demulsifier in the" castor oil is describedin U. S. Patent No. 2,023,979,

resolution of crude oil emulsions. dated December 10, 1935, to stehr, Also se 3,

Another object of our invention is to provide a lo PatentNo. 2,183,487, dated December 12, 1939, to practicable method for manufacturing said new Colbeth.

, chemical product or compound. Thus, the same 'conventionalprocedure or pro- Although one of the primary objects of our dllr S p y d for oxidation of castor oil or invention is to provide a new compound or comsimilar compounds is equally suitable for the position of matter that is an efllcient demulsifier l5 blowing o x ion f hyd o yacetylated trig d 11 emulsions of th wat r-mil typ'e, ricinolein. Inmost instances, the period of oxidathe said compound or composition of matter is en m y e mewh lon er, al h h it is also adapted for use in other arts, as hereinafter in- P i to Obtain Satisfactory Products, in whi h dicated. It also may have addltional uses in varthe period of oxidation is somewhat reduced in m other fields which have t ygt b i tino comparison with the oxidation of castor' oil or tri gam ricinolein under the same conditions. The appli- The composition. of matter herein described, cation of oxidation is so similar to or identical particularly when it is intended to be,used as a h that of c or il. at n ifierences of demulsifler for petroleum emulsions of the waterma p l which y be required are p rin-oil type, is obtained by'blowln'g or oxidation ly pp r n n t Or ry conduct of the of hydroxyacetylated ricinoleic compounds, .par- P For ins nc f O e attempts to oxidize ticularly, triricinolein and hydroxyacetylated cas'-' ydrexyace yl ted eastor oil to obtain the same tor oil. The manner oi blowing or oxidizing such Viscosity a an Oxi c r oil. n if at the products is substantially the same as is employed end o t e dete i e pe i the i co i y or to oxidize or blow castor oil, ricinoleic acid, and other index indicates under-oxidation. n t r t k the processis continued until the same or a comt well known th t oxidized ns c n be parable degree of oxidation obtained. Sinaitained from castor oil, ricinoleic acid and various larly. inthe conventional blowing of castor' oil,

derivatives of ricinoleic acid, such as monoricjnthe last'stage 'Of'OXidfllJiOtl is somewhat critical olein, diricinolein and polyricinoleic acids. They d sometim s t p i d o low n must be are produced by the common practice of blowing o t n d. If, .during the oxidation of hy ro yor oxidizing castor oil and similar fatty oils-or .acetylated caster th p n tobe an inacids, particularly non-drying unsaturated fatty Greased Or i en iv p ri Of reaction, obviousl oils, by means of a gaseous medium, such as air, -0nly the ordinary=precautions need be taken to oiqgen, ozone, or ozonized air. The gaseous medi- 40 prevent over-oxidation. Except for the difference um, such as air, may be moist or dry and the in molecularweight, hydroxyacetylated castor oil oxidation may take placedn the presence or abpresents the same degree of-unsaturationas castor senee of a, catalyst, The catalyst may be of a oil, and thus the degree of oxidation can be measmetilllle l Such as lead ricinoleate, cobalt ured,- or at least approximated, by the percentage .rieinoleam'maneee n m e m; or 11-, may reduction in iodine value, simultaneously with the be otthe oraanic type whichproduces peroxide, i r se in viscosity. f

such as alpha-pinene, linseed oil, etc. Oxidation The Pm io nof hydroxyacetylated castor may take place at atmospheric pressure or su'per- Oil is comparatively s mpl n i mp ra le to atmospheric pressure, i. e., pressures up to ,or inthe manufacture of 'acetylated castor (all, except eluding 200 pounds gauge pressure. and at anythat hydroxyacetic acid-appears to be more retemperature slightly above the boiling point of fic v n acetic acid. tor instance, any suitably water, Imam, .c up t any temperselected amount or castor oil may be treated ature-wliich does not produce undue decomposiwith the appr priate amount of hydroxyacetic 111011 Y-Dmlytic reaction. acid under conditions to promote esterincation The time of blowin: may be iairly brie, in: as d e 'l y water termed. The usual weknown, and involve one or more of the following: Employment of a temperature high enough to eliminate any water formed, for instance, 120-180 C.'; sometimes the presence of a strong acid,.such as. a benzene-sulionic acid in small amounts acts as a catalyst; sometimes it is expedient to pass an inert dried gas through the reacting mixture; at other times esterification may be conducted in the presence of a high boiling water-insoluble solvent, such as xylene or the like, which assists in removing the water in the form of vapors; the condensate so derived, both from the water vapor and solvent vapor is separated by gravity; and the solvent returned to the reacting chamber for further use.

The selection of suitable amounts of reactants this is immaterial for the present purpose, On

the average, castor oil will indicate 85-92% or triricinolein. For convenience in the present in stance, one may consider triricinolein as if it were a trihydric alcohol, and thus, one may obtain mono-hydroxyacetylated triricinolein, di-hydroxyacetylated triricinolein, and tri-hydroxyacetylated trii'icinolein. For practical purposes, of course, there is economical justiflcation for trying to obtain a technically pure triricinolein and subjecting such material to hydroxyacetylation instead of employing castor oil.

the product particularly contemplated as a reactant in the present instance, is the compound or compounds obtained by thehydroxyacetylation of castor oil. For purpose of convenience, reference will be made to monohydroxyacetylated castor oil, di-hydroxyacetylated'cas tor oil, and tri-hydroxyacetylated castor oil. Examination of the reaction between hydroxyacetlc acid and castor oil indicates that water is formed and must be removed. Actually, the water formed may not necessarily be removed instantly, and thus may undergo certain other obvious reac- 1, preceding, except that three times the amount of hydroxyacetylated castor oil is employed so as" asvasas 'cedures for promotion or esterification are well Hvnnoxrscrmsm Cssron On.

Example 1 constructed or any material which is resistant to I the reactants. The amount 01 hydroxyacetic acid selected in the present instance is calculated so as to give substantially a mono-hydroxyacetylated castor oil.

Hrnsoxrsclrrmrsn Cssroa On.

' Example 2 The same procedure is employed as in Example 1, preceding, except that twice the amount of hydroxyacetic acid is employed so as to obtain a dijhydroxyacetylated castor oil.

Hxnnoxflcnmrsn Cssroa 011.

Example 3 The same procedure isiollowed as in Example to yield a substantially tri-hydroxyacetylated castor oil,

HYnsoxYscIrYLArsn Cssroa On. Example 4 v The same procedure is followed as in Examples 40 1 to 3, preceding, except that anhydrous hydroxyor more especially, hydroinracetylate'd triricinolein, in the presence of a minimum amount of tions. Likewise, for reasons of economy, it may be desirable to use a highly concentrated hydrox'yacetic acid instead of the anhydrous material as the selected reactant. In such instances. the water would readily enter into hydrolytic reaction with the castor oil, and thus, the product or composition which is actually acetylated may even contain glycerol, in addition to triricinolein. It is not intended, in the present instance, to

hydroxyacetylated cogeners. I Itjs well known that the exact composition of ordinary oxidized castor oil is not known. This has been a matter of comment from time to time in the literature, including the patent literature dealing with arts in which blown castor oil is contemplated. However, it is obvious that the nature of the products obtained by oxidation of hydroxyacetylated triricinolein or castor oil, must be significantly different from those obtained by the oxidation or castor oil. There are a numclaim the product obtained by oxidatlonoi' hyadroxyacetylated derivatives of. ricinoleic acidv compounds. These are now suitablyqualifled to be limited to triricinoiein; dlrlcinolein, m9no-' ricinolein, and ricinoleic acid, and most particularly, the cogeneric mixture'obtain'ed by the hydroxyacet'ylation or castor oil, including specific members mentioned subsequently.

Although it is believed that' in view of what 5 has been said, that noiurther description is necessary in regard to the manufacturejoi hydroxy-' acetylated castor oil, the following examples are included by way or illustration:

her or'reasons for this statement. One. reason present are secondaryalcoholic radicals.

In the case of hydroxyacetylated castor oil, at

, least one of the three alcoholic radicals present "are primary alcoholic radicals, and-all three may be primary alcoholic radicals. Itis one oithe fundamental principles of organic chemistry that the oxidation or primary alcohols yields different 3 products than are obtained by the oxidation of secondary alcohols. In; view of this'single concept alone, it is obvious-that oxidized hydroxyacetylated triricinolein or castor oil must be 0! .a different nature than ordinary oxidized castor In examining the chemical structure of hydroxyaceticaciditis instantly recognized that --s,s.7a,22s the hydroxyl radical present has replaced an alpha-hydrogen atom, and thus, in thelight of the theory of electronegativity, must be particularly susceptible to reaction. This points to a reactiveness on the part of this particular radical which would not necessarily be enjoyed by any primary alcoholic radical.

Then too, previous reference has been made to the fact that one need not employ anhydrous hydroxyacetic acid, but-one may employ a concentrated aqueous solution of the kind available commercially. Thus, water enters as a re;- actant,'even though not necessarily so selected. Hence, ultimately one may be concerned with the oxidation of the cogeneric mixture previously described in detail. Incidentally, in such cogeneric mixtures, not only may ricinoleic acid 'be present, as has been pointed out, but one may also have a poiyricinoleic acid, such as diricinoleic acid, triricinoleic acid,,etc. Such polyricinoleicacids are included within the scope of the expression ricinoleic acid compound, previously employed.

DRASTICALLY-OXIDIZElJ Hxnnoxxscsrym'rsn V Css'rox On.

Example 1 1,000 pounds of a material of the kind described under the heading Hydroxyacetylated castor 011,

Example 1, preceding, is subjected to oxidation in the same conventional manner as employed expression does not contemplate wet oxidation,

for castor oil. The temperature-employed'is 120 C., and the time approximately 223 hours. At the end of a period of oxidation, the product 1 shows a marked increase in viscosity. The usual analytical determinations, such. as are conventionally employed in connection-with the examination of blown castor oil, indicate that drastic oxidation has taken place. The values,

so determined, may be conveniently compared with the similar values determined on the hydroxyacetylated castor oil prior to oxidation.

Example 2 The same procedure is followed as in Example 1, preceding, except that one employs as an in-'- termediate material for oxidation the particularhydroxyacetylated castor oil described under the our preference, :by far, isto employ castor oil asa reactant. I a

In view of what'has been said, it is obvious that in the hereto appended claims there cannot be any satisfactory means of characterizing the products, as such, or for use as demulsiflers, except in terminology, which is related to the method of manufacture. I

The expression -drastlcally-oxidized" or drastic oxidation," .as employed in the hereto appended claims, refers -to gaseous oxidation by means of anoxygen-containing medium. Such or oxidation by means of permanganate, or other comparable oxidizing agents.

. It is furthermore understood tha't'hydroxy acetylation can be,conducted by means of the chemical eqhivalent of hydroxyacetic acid, as

well as the acid itself, forexample, the anhydride or acylchloride.

Attention is directed to the fact that the products herein described as being obtained by the hydroxyacetylation of castor oil by the use-of either anhydrous hydroxyacetic acid, or the stronger aqueous solution, results in compounds of the kind disclosed in detail. Such products include, among others, monoand poly-hydroxyacetylated castor. oil, monoand poly-hydroxyacetylated triricinolein, monoand D lie.

hydroxyacetylated superglycerinated castor. oil,

monoand poly-hydroxyacetylatedmonoricinolein, monoand poly-hydroxyacetylated diricinolein, monoand poly-hydroxyacetylated castor oil estolides (see U. S. Patent No. 2,079,762, dated May 11, 1937, to De Groote &-Keiser), hydroxy-' acetylated ricinoleic acid, hydroxyacetylated heading Hydroxyacetylated castor oil, Example 2, preceding. v

' DimsrrcALtY-oxmznn Hxnxoxncsrnusn Casros On.

Example 3 The same procedure is followed as in Example 1, preceding, except that one employs as an intermediate'material for oxidation, the particular hydroxyacetylated castor oil-described under the heading Hydroxyacetylated castor oil, Ex-

ample 3, preceding.

DxAsrmAnLY-oxmrznn Hxmioxxscsmsrsn Cssron On.

, Example 4 The same procedure is followed as in Example 1, preceding, except that one employs as an in- I termediate material for oxidation, the particular hydroxyacetylated castor oil described under the heading Hydroxyacetylated castor oil, Example 4, preceding.

Nothing that hasbeen said previously is intended to suggest that one may not use chemipolyricinoleic acid, etc. As far as we are aware, all of such products, or at least certain specific members, are boldly new chemical com pounds, or new compositions of matter. We have prepared and have in course of preparation, a number of other derivatives in which hydroxyacetylated castor oil or its equivalent serves. as an intermediate material for subse quent reaction with some reactant other than oxygen as in the present instance. S uchother reactants include, amon'g'others, inorganic polybasic acids, including sulfuric acid, phosphoric acid, etc., polybasic carboxy acids, such as phthalic acid, maleic acid, etc., ammonia, amines,

etc.,andother reactants which result in amino derivatives, polyamino derivatives, amido derivatives, poly-amido derivatives, esterifled alkanolamines, quaternary compounds, oxyalkylation derivatives, etc., but specifically'excluding the type analogous to that disclosed in co-pending application of Charle M. Blair, Jr., Serial No. 353,127, filed August 1 1940, which has now matured into Patent No. 2,306,775, dated December 29, 1942.

The herein described chemical compounds or products are of distinct value as a break inducer in the doctor treatment oi' zasoline or the .like, as described in U. 8. Patent No. 2,157,223,

aavaaaa' 2. A drastically-oxidized hydroxyacetylated castor oil.

3. A drastically-oxidized tri-hydroxyacetylated castor oil.

4. In the manufacture of the compound described in claim 1, the steps of: (a) hydroxyacetylation of ricinoleic compounds selected from the class consisting of castor oil, triricinolein, diricinolein, monoricinolein, superglycerinated castor oil, castor oil estolides, polyricinoleic acid and ricinoleic acid; and (b) drastic oxidation of the same.

MELVIN DE GROOTE. BERNHARD KEISER. ARTHUR F. -WIRTEL. 

